CN112264096B - Magnetic Fenton-like catalyst based on chitosan and preparation method and application thereof - Google Patents

Magnetic Fenton-like catalyst based on chitosan and preparation method and application thereof Download PDF

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CN112264096B
CN112264096B CN202011326427.2A CN202011326427A CN112264096B CN 112264096 B CN112264096 B CN 112264096B CN 202011326427 A CN202011326427 A CN 202011326427A CN 112264096 B CN112264096 B CN 112264096B
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杨金帆
敖志锋
牛晓茹
张素风
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Shaanxi University of Science and Technology
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Abstract

The invention provides a magnetic Fenton-like catalyst based on chitosan and a preparation method and application thereof, wherein chitosan is dissolved in an acetic acid solution, then manganese salt, ferric salt and ferrous salt are added and stirred to obtain a uniformly dispersed salt solution A, and sodium hydroxide and sodium acetate are dissolved in water to form an alkali solution B; dropwise adding the salt solution A into the alkali solution B at a constant speed, and after dropwise adding is finished, placing the obtained mixed solution into a constant-temperature oscillator for oscillation and aging to obtain CH-Mn-Fe gel beads; washing the CH-Mn-Fe gel beads to be neutral, and freeze-drying to obtain the magnetic microsphere MnO with the porous structure 2 ‑Fe 3 O 4 a/CH composite catalyst. Avoids the agglomeration of metal particles, inhibits the metal loss, is extremely easy to recover, and has simple preparation process.

Description

Magnetic Fenton-like catalyst based on chitosan and preparation method and application thereof
Technical Field
The invention relates to the technical field of magnetic catalyst preparation, in particular to MnO 2 -Fe 3 O 4 A chitosan composite magnetic microsphere, a one-step in-situ preparation method and application thereof.
Background
The dye is widely applied to the industries of synthesis, spinning, cosmetics, printing and the like, and the problem of serious environmental pollution is caused by the discharge of a large amount of industrial dye wastewater. Methylene blue is one of the most common dyes and has been shown to cause a variety of human diseases. Therefore, the removal of methylene blue from water is of great importance. There are many methods for removing dyes from water, and among them, advanced oxidative degradation technology has attracted much attention because of its advantages such as simplicity and high efficiency. The fenton method is a classical advanced oxidative degradation technique: namely hydrogen peroxide (H) 2 O 2 ) And ferrous ion (Fe) 2+ ) The mixtures of (a) oxidize many organic compounds, such as carboxylic acids, alcohols and esters, to harmless chemicals. However, the application of the conventional Fenton method is subject to the pH range (2E)4) The catalyst is narrow, the catalyst is not easy to separate and recycle from the waste water after the reaction, and a large amount of iron mud is generated to cause the defects of secondary pollution and the like. In order to solve the above problems, efforts have been made to develop heterogeneous fenton-like systems: using metal oxides instead of Fe 2+ As a reaction catalyst. The use of a heterogeneous fenton-like system has the following advantages: (1) the application range is wide, and the degradation rate is high; (2) The catalyst is easy to separate and recycle, and secondary pollution is avoided.
The electron transfer is an important process of a heterogeneous Fenton-like catalytic system, so that the nano manganese dioxide (MnO) with multiple oxidation states 2 ) And nano ferroferric oxide (Fe) 3 O 4 ) Is an ideal heterogeneous Fenton-like catalyst. However, the direct use of these nano metal catalysts causes the following problems: (1) agglomeration phenomenon. The effective active area of the catalyst is reduced and thus the catalytic efficiency is reduced. And (2) metal loss. The leaching of metal ions leads to the reduction of active components and simultaneously brings secondary pollution to water. (3) recovery is difficult. Powdered nano metal has higher hydrophilicity, and needs to be centrifuged or filtered in a laboratory to be recycled, so that the actual application cost is increased. These problems above limit the nano-MnO to a great extent 2 And Fe 3 O 4 Industrial application of (1).
Nano MnO 2 And nano Fe 3 O 4 The synergistic effect of (A) contributes to the improvement of the degradation efficiency, and at present most of MnO is 2 -Fe 3 O 4 The preparation method of the composite catalyst is a two-step hydrothermal method, and ferrous sulfate (FeSO) is firstly used 4 ) Raw materials are synthesized into nano Fe by a hydrothermal method 3 O 4 Then potassium permanganate (KMnO) is added 4 ) With nano Fe 3 O 4 MnO is obtained after mixed hydrothermal treatment 2 -Fe 3 O 4 Composite catalyst (Chemical Engineering Journal,2019,357 (337-347)). The preparation method has complicated steps, and the obtained composite catalyst has nanometer MnO due to the unsaturation and instability of the surface of the nanometer particles 2 And Fe 3 O 4 The particles are easy to aggregate and not beneficial to activate H 2 O 2 。
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a magnetic Fenton-like catalyst based on chitosan, a one-step in-situ preparation method and application thereof, which avoid the agglomeration of metal particles, inhibit the metal loss, are easy to recover and have a simple preparation process.
The invention is realized by the following technical scheme:
a preparation method of a magnetic Fenton-like catalyst based on chitosan comprises the following steps:
dissolving chitosan in an acetic acid solution, adding manganese salt, ferric salt and ferrous salt, stirring to obtain a uniformly dispersed salt solution A, and dissolving sodium hydroxide and sodium acetate in water to form an alkali solution B; dropwise adding the salt solution A into the alkali solution B at a constant speed, and after dropwise adding is finished, placing the obtained mixed solution into a constant-temperature oscillator for oscillation and aging to obtain CH-Mn-Fe gel beads; washing the CH-Mn-Fe gel beads to be neutral, and freeze-drying to obtain the magnetic microsphere MnO with the porous structure 2 -Fe 3 O 4 a/CH composite catalyst.
Preferably, the mass volume ratio of the chitosan to the acetic acid is 1g: (0.1-1) mL, and the concentration of the acetic acid solution is 0.25-2.5 wt%.
Preferably, the manganese salt is one of manganese nitrate, manganese sulfate and manganese chloride; the ferrous salt is one of ferrous nitrate, ferrous sulfate and ferrous chloride; the iron salt is one of ferric nitrate, ferric sulfate and ferric chloride.
Preferably, the mass molar ratio of the chitosan to the manganese salt is 1g: (0.001-0.02) mol, and the molar ratio of manganese salt to iron salt is 1: (0.1-10), and the molar ratio of the ferric salt to the ferrous salt is 2.
Preferably, the concentration of sodium hydroxide in the alkali solution B is 0.1-2M, and the molar ratio of sodium hydroxide to sodium acetate is 1.
Preferably, the dropping speed of the saline solution A and the alkaline solution B which are added dropwise at constant speed is 3-10 mL/min.
Preferably, the temperature of the constant temperature oscillator is 20-80 ℃, the oscillation aging time is 3-24 h, and the freeze drying time is 6-24 h.
Magnetic microsphere MnO obtained by adopting the preparation method 2 -Fe 3 O 4 a/CH composite catalyst.
The magnetic microsphere MnO 2 -Fe 3 O 4 The application of the/CH composite catalyst in catalyzing methylene blue heterogeneous Fenton-like degradation reaction.
Preferably, the oxidant for the heterogeneous Fenton-like degradation reaction of methylene blue is H 2 O 2 ，H 2 O 2 The dosage is 0.1-2M 2 -Fe 3 O 4 The dosage of the/CH composite catalyst is 0.5-5 g/L, and the degradation time is 30-120 min.
Compared with the prior art, the invention has the following beneficial technical effects:
the process of the invention is based on ferromanganese salts and OH - Coprecipitated oxidation (Fe) 2+ +2Fe 3+ +8OH-→Fe 3 O 4 +4H 2 O,2Mn 2+ +4OH-+O 2 →2MnO 2 +2H 2 O) and Chitosan (CH) is subjected to alkali polymerization crosslinking, the two reaction processes are coupled, and the nano MnO is subjected to the next step under an alkali condition 2 And nano Fe 3 O 4 Immobilized in a chitosan network structure to obtain macroscopic magnetic microspheres MnO 2 -Fe 3 O 4 and/CH. abundant-NH on the carbon chain of chitosan 2 and-OH function with Mn 2+ And Fe 3+ And through interaction, the metal oxide is uniformly dispersed in situ in a network structure generated by chitosan crosslinking, so that the agglomeration of metal particles is avoided. Simultaneously, the reactive metal is reacted with-NH 2 The coordination of (2) inhibits metal loss and improves the stability of the catalyst. Obtained macroscopic magnetic microsphere MnO 2 -Fe 3 O 4 the/CH is millimeter-scale magnetic particles and is easy to recover. MnO (MnO) 2 And Fe 3 O 4 The metal synergistic effect exists between the two, and the transmission of electrons in Fenton-like reaction is promoted, so that MnO is 2 -Fe 3 O 4 The catalytic activity of/CH for Fenton degradation of methylene blue is obviously higher than that of a single metal catalyst (MnO) 2 /CH or Fe 3 O 4 /CH). The invention can be prepared in one step, the preparation process is mild, the process is simple, the operation is easy, and the cost of the chitosan serving as the raw material is lower.
Drawings
FIG. 1 one-step in-situ preparation of magnetic microsphere MnO 2 -Fe 3 O 4 Flow diagram of/CH.
FIG. 2 magnetic microsphere MnO 2 -Fe 3 O 4 a/CH: before (A) freeze-drying and after (B) freeze-drying.
FIG. 3MnO 2 /CH、Fe 3 O 4 [ CH ] and MnO 2 -Fe 3 O 4 XRD diffractogram of/CH sample.
FIG. 4MnO 2 -Fe 3 O 4 Of the/CH samples: (A) N is a radical of hydrogen 2 Adsorption-desorption isotherms, and (B) size distribution curves.
FIG. 5 is a comparison of the images before and after Fenton-like degradation of methylene blue solution.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The method of the invention is that alkaline coprecipitation of manganese salt, ferric salt and ferrous salt is carried out to form nano-particles in situ in a polymer matrix, and the magnetic chitosan gel micro-beads are formed after common aging. No MnO has been found yet by searching domestic and foreign documents 2 -Fe 3 O 4 The coprecipitation process is coupled with the alkali polymerization process of the chitosan, and MnO is synthesized in situ by one step 2 -Fe 3 O 4 A preparation method of a/CH composite catalyst.
As shown in fig. 1, the preparation method of the invention specifically comprises the following steps:
(1) Weighing 1g of chitosan, fully dissolving the chitosan in 40mL of 0.25-2.5 wt% acetic acid solution, sequentially adding 0.001-0.02 mol of manganese salt, 0.0001-0.2 mol of ferric salt and 0.00005-0.1 mol of ferrous salt, and fully dissolving to obtain a salt solution A. 0.01 to 0.2mol of sodium hydroxide and 0.01 to 0.2mol of sodium acetate are weighed and dissolved in 100mL of deionized water to form an alkali solution B. Dropwise adding the salt solution A into the alkali liquor B at a constant speed of 3-10 mL/min. After the dropwise addition is finished, the obtained mixed solution is placed in a constant temperature oscillator at the temperature of 20-80 ℃ for oscillation and aging for 3-24 hours to obtain the composite gel microbeads. Washing the gel microspheres with deionized water to neutrality, and freeze-drying for 6-24 h to obtain the magnetic microspheres with porous structuresMnO 2 -Fe 3 O 4 a/CH hybrid catalyst.
The manganese salt is one of manganese nitrate, manganese sulfate and manganese chloride; the ferrous salt is one of ferrous nitrate, ferrous sulfate and ferrous chloride; the iron salt is one of ferric nitrate, ferric sulfate and ferric chloride.
Magnetic microsphere MnO as described above 2 -Fe 3 O 4 the/CH is used for catalyzing the Fenton-like degradation of methylene blue heterogeneous phase and comprises the following steps: firstly, magnetic microspheres MnO are added 2 -Fe 3 O 4 Mixing the/CH with the dye solution, and adding hydrogen peroxide to carry out Fenton-like degradation reaction. Wherein the concentration of methylene blue is 10-500 mg/L, and the oxidant H 2 O 2 The dosage is 0.1-2M, and the magnetic microsphere MnO is 2 -Fe 3 O 4 The dosage of the/CH is 0.5-5 g/L, and the degradation time is 30-120 min.
Example 1
Weighing 1g of chitosan, fully dissolving the chitosan in 40mL of 0.25wt% acetic acid solution, sequentially adding 0.001mol of manganese nitrate, 0.2mol of ferric nitrate and 0.1mol of ferrous nitrate, and keeping magnetic stirring until the chitosan is fully dissolved to obtain a uniformly dispersed salt solution A. 0.01mol of sodium hydroxide and 0.01mol of sodium acetate are weighed out and dissolved in 100mL of deionized water to form an alkali solution B. Dropwise adding the salt solution A into the alkali solution B at a constant speed of 3mL/min, and after dropwise adding, placing the obtained mixed solution into a constant temperature oscillator at 20 ℃ for oscillation aging for 3h to obtain CH-Mn-Fe gel beads as shown in figure 2 (A). Washing the CH-Mn-Fe gel beads to be neutral, and freeze-drying for 6h to obtain the magnetic microsphere MnO with the porous structure 2 -Fe 3 O 4 The particle diameter of the/CH composite catalyst is 2-4mm as shown in FIG. 2 (B).
By wide angle XRD (FIG. 3), mnO 2 -Fe 3 O 4 the/CH corresponds to MnO at 2 θ =19.2 °, 36.9 °, and 50.2 °, respectively 2 The (111), (311) and (331) planes of (JCPDS No. 44-0992); fe at 2 θ =30.2 °, 35.6 °, 43.3 °, 57.1 ° and 62.8 °, respectively 3 O 4 The (220), (311), (400), (511) and (440) faces (JCPDS No. 19-0629). This indicates MnO 2 -Fe 3 O 4 Successful preparation of the/CH composite catalyst. Further, mnO 2 -Fe 3 O 4 N of/CH 2 The adsorption-desorption isotherm (fig. 4 (a)) is type IV of the H3 hysteresis cycle, which clearly indicates the presence of mesopores. Pore size distribution curve (FIG. 4 (B)) shows MnO 2 -Fe 3 O 4 the/CH is distributed in micro/meso/macropores, and the size is mainly between 20 and 100 nm.
Measuring 100mL10 mg/L methylene blue solution in an erlenmeyer flask, adding 0.01mol H 2 O 2 And 0.5g of magnetic microsphere MnO prepared above 2 -Fe 3 O 4 and/CH, stirring and reacting for 30min at room temperature. The degradation rate of methylene blue is 75.5 percent by the analysis of an ultraviolet visible light spectrophotometer. After the reaction is finished, the catalyst is separated by a magnet (figure 5), the catalyst is fully washed, then is frozen and dried overnight, the cycle test is carried out under the same condition, and the degradation rate can still reach 69.4 percent after three continuous degradation reactions. The catalyst proved to have good stability.
Example 2
Weighing 1g of chitosan, fully dissolving the chitosan in 40mL of 1.0wt% acetic acid solution, sequentially adding 0.005mol of manganese sulfate, 0.025mol of ferric nitrate and 0.0125mol of ferrous nitrate, and keeping magnetic stirring until the chitosan is fully dissolved to obtain a uniformly dispersed salt solution A. 0.05mol of sodium hydroxide and 0.05mol of sodium acetate are weighed out and dissolved in 100mL of deionized water to form the alkali solution B. Dropwise adding the salt solution A into the alkali solution B at a constant speed of 5mL/min, and after dropwise adding, placing the obtained mixed solution into a constant-temperature oscillator at 40 ℃ for oscillation aging for 8h to obtain CH-Mn-Fe gel beads. Washing the CH-Mn-Fe gel beads to be neutral, and freeze-drying for 12h to obtain the magnetic microsphere MnO with the porous structure 2 -Fe 3 O 4 a/CH hybrid catalyst.
Measuring 100mL50 mg/L methylene blue solution in an erlenmeyer flask, adding 0.05mol of H 2 O 2 And 2.0g of magnetic microsphere MnO prepared as above 2 -Fe 3 O 4 and/CH, stirring and reacting for 60min at room temperature. The degradation rate of methylene blue is 90.7 percent by the analysis of an ultraviolet visible light spectrophotometer. After the reaction is finished, separating the catalyst by using a magnet, fully washing, freeze-drying overnight, carrying out cycle test under the same condition, and continuously degrading for three timesAfter the reaction, the degradation rate can still reach 87.2 percent. The catalyst proved to have good stability.
Embodiment 3
Weighing 1g of chitosan, fully dissolving the chitosan in 40mL of 2.0wt% acetic acid solution, sequentially adding 0.01mol of manganese chloride, 0.02mol of ferric chloride and 0.01mol of ferrous chloride, and keeping magnetic stirring until the chitosan is fully dissolved to obtain a uniformly dispersed salt solution A. 0.1mol of sodium hydroxide and 0.1mol of sodium acetate are weighed out and dissolved in 100mL of deionized water to form the alkali solution B. Dropwise adding the salt solution A into the alkali solution B at a constant speed of 7mL/min, and after dropwise adding, placing the obtained mixed solution into a constant-temperature oscillator at 50 ℃ for oscillation aging for 12h to obtain CH-Mn-Fe gel beads. Washing the CH-Mn-Fe gel beads to be neutral, and freeze-drying for 16h to obtain the magnetic microsphere MnO with a porous structure 2 -Fe 3 O 4 a/CH composite catalyst.
Measuring 100mL100 mg/L methylene blue solution in an erlenmeyer flask, adding 0.1mol H 2 O 2 And 3.0g of magnetic microsphere MnO prepared as above 2 -Fe 3 O 4 and/CH, stirring and reacting for 80min at room temperature. The degradation rate of methylene blue is 100% by the analysis of an ultraviolet-visible light spectrophotometer. After the reaction is finished, separating the catalyst by a magnet, fully washing, freeze-drying overnight, and carrying out cycle test under the same condition, wherein the degradation rate can still reach 98.2% after three continuous degradation reactions. The catalyst proved to have good stability.
Example 4
Weighing 1g of chitosan, fully dissolving the chitosan in 40mL of 4.0wt% acetic acid solution, sequentially adding 0.015mol of manganese nitrate, 0.015mol of ferric nitrate and 0.0075mol of ferrous nitrate, and keeping magnetic stirring until the chitosan is fully dissolved to obtain a uniformly dispersed salt solution A. 0.15mol of sodium hydroxide and 0.15mol of sodium acetate are weighed out and dissolved in 100mL of deionized water to form the alkali solution B. Dropwise adding the salt solution A into the alkali solution B at a constant speed of 9mL/min, and after dropwise adding, placing the obtained mixed solution into a constant-temperature oscillator at 70 ℃ for oscillation aging for 18h to obtain CH-Mn-Fe gel beads. Washing the CH-Mn-Fe gel beads to be neutral, and freeze-drying for 20 hours to obtain the magnetic microsphere MnO with a porous structure 2 -Fe 3 O 4 /CH composite catalystAn oxidizing agent.
Measuring 100mL250 mg/L methylene blue solution in an erlenmeyer flask, adding 0.15mol H 2 O 2 And 3.0g of magnetic microsphere MnO prepared as described above 2 -Fe 3 O 4 and/CH, stirring and reacting for 100min at room temperature. The degradation rate of methylene blue is 98.3 percent by the analysis of an ultraviolet visible light spectrophotometer. After the reaction is finished, separating the catalyst by using a magnet, fully washing, freezing and drying overnight, carrying out a cycle test under the same condition, and carrying out three continuous degradation reactions until the degradation rate still reaches 95.6%. The catalyst proved to have good stability.
Example 5
Weighing 1g of chitosan, fully dissolving the chitosan in 40mL of 5.0wt% acetic acid solution, sequentially adding 0.01mol of manganese chloride, 0.0001mol of ferric sulfate and 0.00005mol of ferrous nitrate, and keeping magnetic stirring until the chitosan is fully dissolved to obtain a uniformly dispersed salt solution A. 0.2mol of sodium hydroxide and 0.2mol of sodium acetate are weighed out and dissolved in 100mL of deionized water to form the alkali solution B. Dropwise adding the salt solution A into the alkali solution B at a constant speed of 10mL/min, and after dropwise adding, placing the obtained mixed solution into a constant-temperature oscillator at 80 ℃ for oscillation aging for 24h to obtain CH-Mn-Fe gel beads. Washing the CH-Mn-Fe gel beads to be neutral, and freeze-drying for 24 hours to obtain the magnetic microsphere MnO with a porous structure 2 -Fe 3 O 4 a/CH composite catalyst.
Measuring 100mL500 mg/L methylene blue solution in an erlenmeyer flask, adding 0.2mol H 2 O 2 And 5.0g of magnetic microsphere MnO prepared above 2 -Fe 3 O 4 and/CH, stirring and reacting for 120min at room temperature. The degradation rate of methylene blue is 95.8 percent by the analysis of an ultraviolet visible light spectrophotometer. After the reaction is finished, separating the catalyst by a magnet, fully washing, freeze-drying overnight, and carrying out cycle test under the same condition, wherein the degradation rate can still reach 92.4% after three continuous degradation reactions. The catalyst proved to have good stability.

Claims (8)

1. A preparation method of a magnetic Fenton-like catalyst based on chitosan is characterized by comprising the following steps:
dissolving chitosan in an acetic acid solution, adding manganese salt, ferric salt and ferrous salt, stirring to obtain a uniformly dispersed salt solution A, and dissolving sodium hydroxide and sodium acetate in water to form an alkali solution B; dropwise adding the salt solution A into the alkali solution B at a constant speed, and after dropwise adding is finished, placing the obtained mixed solution into a constant-temperature oscillator for oscillation and aging to obtain CH-Mn-Fe gel beads; washing the CH-Mn-Fe gel beads to be neutral, and freeze-drying to obtain the magnetic microsphere MnO with the porous structure 2 -Fe 3 O 4 a/CH complex catalyst;
the mass molar ratio of the chitosan to the manganese salt is 1g: (0.001-0.02) mol, wherein the molar ratio of manganese salt to iron salt is 1: (0.1-10), wherein the molar ratio of ferric salt to ferrous salt is 2;
the temperature of the constant temperature oscillator is 20-80 ℃, the oscillation aging time is 3-24 h, and the freeze drying time is 6-24 h.
2. The method for preparing a magnetic fenton-like catalyst based on chitosan according to claim 1, wherein the mass volume ratio of chitosan to acetic acid is 1g: (0.1-1) mL, and the concentration of the acetic acid solution is 0.25-2.5 wt%.
3. The method of preparing a chitosan-based magnetic fenton-like catalyst according to claim 1, wherein the manganese salt is one of manganese nitrate, manganese sulfate and manganese chloride; the ferrous salt is one of ferrous nitrate, ferrous sulfate and ferrous chloride; the iron salt is one of ferric nitrate, ferric sulfate and ferric chloride.
4. The method for preparing a magnetic fenton-like catalyst based on chitosan according to claim 1, wherein the concentration of sodium hydroxide in the alkali solution B is 0.1 to 2M, and the molar ratio of sodium hydroxide to sodium acetate is 1.
5. The preparation method of the chitosan-based magnetic Fenton-like catalyst according to claim 1, wherein the dropping speed of the alkaline solution B added dropwise at a constant speed of the salt solution A is 3-10 mL/min.
6. The chitosan-based magnetic Fenton-like catalyst obtained by the preparation method according to any one of claims 1 to 5.
7. Use of the chitosan-based magnetic Fenton-like catalyst of claim 6 for catalyzing methylene blue heterogeneous Fenton-like degradation reactions.
8. The use according to claim 7, wherein the oxidizing agent for the heterogeneous Fenton-like degradation reaction of methylene blue is H 2 O 2 ，H 2 O 2 The dosage is 0.1-2M 2 -Fe 3 O 4 The dosage of the/CH composite catalyst is 0.5-5 g/L, and the degradation time is 30-120 min.
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